# US 9,434,666 B2 · Catalytic hydrogenation using complexes of base metals with tridentate ligands

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- Number: US 9,434,666 B2
- Document ID: US9434666B2
- Status: Granted
- Kind: B2
- Application number: 13/587,717
- Filed: 2012-08-16
- Published: 2015-11-26
- Granted: 2016-09-06
- Earliest claimed: 2012-08-16
- Assignees: Los Alamos National Security, LLC
- Applicants: Kalyan V. Vasudevan; Guoqi Zhang; Susan K. Hanson
- Inventors: Kalyan V. Vasudevan; Guoqi Zhang; Susan K. Hanson
- Web page: https://patentgrep.com/patent/US9434666B2

## CPC

- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- B01J 31/189: {containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand}
- B01J 31/2476: {comprising aliphatic or saturated rings}
- C07C 5/03: of non-aromatic carbon-to-carbon double bonds
- C07C 5/05: Partial hydrogenation
- C07C 17/354: by hydrogenation
- C07C 29/141: with hydrogen or hydrogen-containing gases
- C07C 29/145: with hydrogen or hydrogen-containing gases
- C07C 29/172: {with the obtention of a fully saturated alcohol}
- C07C 29/175: {with simultaneous reduction of an oxo group}
- C07C 41/01: Preparation of ethers
- C07C 41/18: by reactions not forming ether-oxygen bonds
- C07C 41/20: by hydrogenation of carbon-to-carbon double or triple bonds
- C07C 41/26: by introduction of hydroxy or O-metal groups
- C07C 45/62: by hydrogenation of carbon-to-carbon double or triple bonds
- C07C 51/36: by hydrogenation of carbon-to-carbon unsaturated bonds
- C07C 67/303: by hydrogenation of unsaturated carbon-to-carbon bonds
- C07C 209/52: by reduction of imines or imino-ethers (C07C209/24 takes precedence)
- C07C 209/70: by reduction of unsaturated amines
- C07D 211/02: Preparation by ring-closure or hydrogenation
- C07D 211/46: having a hydrogen atom as the second substituent in position 4
- C07F 5/04: Esters of boric acids
- C07F 15/04: Nickel compounds
- C07F 15/045: {without a metal-carbon linkage}
- C07F 15/06: Cobalt compounds
- C07F 15/065: {without a metal-carbon linkage}
- B01J 2231/643: of R2C=O or R2C=NR (R= C, H)
- B01J 2231/645: of C=C or C-C triple bonds
- B01J 2231/646: of aromatic or heteroaromatic rings
- B01J 2531/0244: Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
- B01J 2531/845: Cobalt
- B01J 2531/847: Nickel
- C07C 2531/14: of aluminium or boron
- C07C 2531/22: Organic complexes
- C07C 2531/28: of the platinum group metals, iron group metals or copper
- C07C 2601/14: The ring being saturated
- C07C 2601/16: the ring being unsaturated
- C07C 2601/18: with a ring being at least seven-membered
- C07C 2602/08: the other ring being five-membered, e.g. indane
- C07C 2602/42: the bicyclo ring system containing seven carbon atoms
- C07C 2603/12: only one five-membered ring
- C07C 2603/18: Fluorenes; Hydrogenated fluorenes
- Y02P 20/52: using catalysts, e.g. selective catalysts
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Complexes of cobalt and nickel with tridentate ligand PNHPR are effective for hydrogenation of unsaturated compounds. Cobalt complex [(PNHPCy)Co(CH2SiMe3)]BArF4 (PNHPCy=bis[2-(dicyclohexylphosphino)ethyl]amine, BArF4=B(3,5-(CF3)2C6H3)4)) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions (25-60° C., 1-4 atm H2). Nickel complex [(PNHPCy)Ni(H)]BPh4 was used for hydrogenation of styrene and 1-octene under mild conditions. (PNPCy)Ni(H) was used for hydrogenating alkenes.

## Claims

### Claim 1

A composition of the formula
wherein each R1 is independently selected from cycloalkyl, alkyl, substituted alkyl, phenyl, or substituted phenyl;
wherein R2 is —CH2Si(CH3)3, H, alkyl, substituted alkyl, phenyl, substituted phenyl, alkoxide, or amido;
wherein M is cobalt or nickel; and
wherein X is a counterion.

### Claim 2 (depends on 1)

The composition of claim 1, wherein the counterion X is tetraphenylborate, hexafluorophosphate, B(C6F5)4, or B(3,5-(CF3)2C6H3)4.

### Claim 3 (depends on 2)

The composition of claim 2, wherein M is cobalt, R2 is —CH2Si(CH3)3, and X is B(3,5-(CF3)2C6H3)4.

### Claim 4 (depends on 2)

The composition of claim 2, wherein M is cobalt, R2 is H, and X is B(3,5-(CF3)2C6H3)4.

### Claim 5 (depends on 2)

The composition of claim 2, wherein M is cobalt, R2 is alkyl, and X is B(3,5-(CF3)2C6H3)4.

### Claim 6 (depends on 2)

The composition of claim 2, wherein M is nickel, R2 is H, and X is tetraphenylborate, hexafluorophosphate, or B(3,5-(CF3)2C6H3)4.

### Claim 7

A composition of the formula
wherein each R1 is independently selected from cycloalkyl, alkyl, substituted alkyl, phenyl, or substituted phenyl;
wherein R2 is —CH2Si(CH3)3, H, alkyl, substituted alkyl, phenyl, substituted phenyl, alkoxide, or amido; and
wherein M is cobalt or nickel.

### Claim 8 (depends on 6)

The composition of claim 6, wherein M is cobalt and R2 is —CH2Si(CH3)3.

### Claim 9 (depends on 6)

The composition of claim 6, wherein M is nickel and R2 is H.

### Claim 10 (depends on 1)

A process for hydrogenation of an unsaturated compound, the process comprising:
combining the composition of claim 1 with hydrogen and an unsaturated compound under conditions effective for the hydrogenation of the unsaturated compound.

### Claim 11 (depends on 10)

The process of claim 10, wherein M is cobalt.

### Claim 12 (depends on 11)

The process of claim 11, wherein R2 is H.

### Claim 13 (depends on 12)

The process of claim 12, wherein the counterion X is B(3,5-(CF3)2C6H3)4.

### Claim 14 (depends on 11)

The process of claim 11, wherein M is nickel.

### Claim 15 (depends on 14)

The process of claim 14, wherein X is B(3,5-(CF3)2C6H3)4.

### Claim 16 (depends on 10)

The process of claim 10, wherein the unsaturated compound comprises a carbon-carbon double or triple bond that becomes hydrogenated as a result of the process.

### Claim 17 (depends on 10)

The process of claim 10, wherein the unsaturated compound comprises a carbon-oxygen double bond that becomes hydrogenated as a result of the process.

### Claim 18 (depends on 10)

The process of claim 10, wherein the unsaturated compound comprises a carbon-nitrogen double or triple bond that becomes hydrogenated as a result of the process.

### Claim 19 (depends on 1)

A process for hydrogenation of an unsaturated compound, the process comprising combining a solution of the composition of claim 1 with hydrogen and an unsaturated compound under conditions effective for the hydrogenation of the unsaturated compound.